US9944582B2 - Method for the purification of acetic acid and acrylic acid - Google Patents

Method for the purification of acetic acid and acrylic acid Download PDF

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Publication number
US9944582B2
US9944582B2 US14/787,683 US201414787683A US9944582B2 US 9944582 B2 US9944582 B2 US 9944582B2 US 201414787683 A US201414787683 A US 201414787683A US 9944582 B2 US9944582 B2 US 9944582B2
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boiling solvent
mixture
crude product
acrylic acid
acetic acid
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US20160075630A1 (en
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Mustapha N. KARIME
Faisal Baksh
Mubarik BASHIR
Zeeshan Nawaz
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Saudi Basic Industries Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C07C51/46—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation by azeotropic distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/08—Acetic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters

Definitions

  • the invention in an aspect, relates to an integrated scheme for purification of acetic acid and acrylic acid present in a crude product mixture, and a method for the manufacture of acrylate monomers, or specialty acrylates, from the purified acrylic acid.
  • FIGURE which is incorporated in and constitute a part of this specification, illustrate several aspects and together with the description serve to explain the principles of the invention.
  • FIG. 1 shows an overall schematic diagram of the integrated process for an aspect of the present invention for purifying mixtures of acetic acid and acrylic acid.
  • Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
  • references in the specification and concluding claims to parts by weight of a particular element or component in a composition denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed.
  • X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
  • a weight percent (wt. %) of a component is based on the total weight of the formulation or composition in which the component is included.
  • the terms “optional” or “optionally” means that the subsequently described event or circumstance can or can not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
  • stable refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain aspects, their recovery, purification, and use for one or more of the purposes disclosed herein.
  • high-boiling solvent refers to a solvent capable of dissolving acetic acid and acrylic acid, with a boiling point greater than the dew point of the gaseous stream containing these acids, i.e., in most cases, when the bulk of the gaseous stream contains water, the boiling point of the high boiling solvent is greater than about 105° C.
  • low-boiling solvent refers to a solvent capable of performing as an entrainer and capable of breaking the acetic acid-water azeotrope, and having a boiling point sufficiently lower than that of acetic acid so that the separation of acetic acid from the solvent can be achieved.
  • specialty acrylate or “specialty acrylates” refers to esters of acrylic acid that have potential value as marketable specialty chemicals or monomers. Examples include 2-ethylhexyl acrylate.
  • Crude product mixture refers to a product mixture that is the output of a reactor that has not been subjected to any substantial purification steps.
  • partial oxidation reaction refers to a reaction of a hydrocarbon with oxygen, generally in the presence of catalyst, which produces oxidation products such as alcohols, aldehydes, and carboxylic acids or mixtures thereof, with lesser amounts of complete oxidation products, i.e., CO 2 and H 2 O.
  • Certain materials, compounds, compositions, and components disclosed herein can be obtained commercially or readily synthesized using techniques generally known to those of skill in the art.
  • the starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers such as Aldrich Chemical Co., (Milwaukee, Wis.), Acros Organics (Morris Plains, N.J.), Fisher Scientific (Pittsburgh, Pa.), or Sigma (St.
  • compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.
  • a method for purifying an acid comprising:
  • the starting materials comprise propane or propylene, or a mixture thereof.
  • the invention comprises a method for producing a crude product mixture by a partial oxidation reaction, wherein the crude product mixture comprises acrylic acid and acetic acid.
  • the crude product mixture can be produced by the partial oxidation reaction of propane by oxygen over a mixed metal catalyst.
  • the oxidation can be carried out using conventional techniques in a reactor, which typically results in an output of a heated crude product stream with temperatures ranging from about 250° C. to about 350° C., including exemplary values of 260° C., 270° C., 280° C., 290° C., 300° C., 310° C., 320° C., 330° C., and 340° C.
  • the temperature can be in a range derived from any two exemplary values.
  • the temperature can range from 260° C. to 340° C.
  • the crude product stream can be then directly introduced into the process as disclosed herein.
  • the partial oxidation reaction refers to a reaction where the complete oxidation of propane, for example a burning reaction of the propane, is avoided.
  • a process for the partial oxidation of propane is recited, for example, in U.S. Pat. No. 5,198,580 and U.S. Pat. No. 6,160,162; all of which are hereby incorporated in its entirety for the specific purpose of disclosing a process for the partial oxidation of propane.
  • the mixed metal catalyst comprises Mo—V—Ga—Pd—Nb—X, where X is La, Te, Ge, Zn, Si, In or W.
  • the mixed metal catalyst can be prepared using conventional catalyst preparation techniques.
  • the products of the partial oxidation reaction comprise propene, acrylic acid, acetic acid, or CO x , where x can be 1 or 2, or a mixture thereof.
  • the crude product mixture comprises acrylic acid in an amount ranging from 1 wt % to 99 wt %, based on the total weight of the crude product mixture, including exemplary values of 2 wt %, 4 wt %, 6 wt %, 10 wt %, 13 wt %, 15 wt %, 17 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt %, 40 wt %, 45 wt %, 50 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %, 80 wt %, 85 wt %, 90 wt %, 95 wt %, 96 wt %, 97 wt %, and 98 wt %.
  • the amount can be in a range derived from any two exemplary values.
  • the crude product mixture comprises acrylic acid in an amount ranging from 2 wt % to 99 wt %, based on the total weight of the crude product mixture.
  • the crude product mixture comprises acetic acid in an amount ranging from 1 wt % to 99 wt %, based on the total weight of the crude product mixture, including exemplary values of 2 wt %, 4 wt %, 6 wt %, 10 wt %, 13 wt %, 15 wt %, 17 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt %, 40 wt %, 45 wt %, 50 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %, 80 wt %, 85 wt %, 90 wt %, 95 wt %, 96 wt %, 97 wt %, and 98 wt %.
  • the amount can be in a range derived from any two exemplary values.
  • the crude product mixture comprises acetic acid in an amount ranging from 2 wt % to 99 wt %, based on the total weight of the crude product mixture.
  • the crude product mixture can optionally comprise a balance amount of one or more additive materials, with the proviso that the additives are selected so as to not significantly adversely affect the desired properties of the crude product mixture.
  • additives can be used. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition.
  • additive materials that can be present in the disclosed crude product mixture include an antioxidant, a stabilizer (including for example a thermal stabilizer, a hydrolytic stabilizer, or a light stabilizer), UV absorbing additive, plasticizer, lubricant, mold release agent, acid scavenger, antistatic agent, or colorant (e.g., pigment and/or dye), or any combination thereof.
  • the purification steps are directed to separating the acrylic acid from the crude product and separating the acetic acid from the crude product.
  • the invention comprises a method for purifying the crude product mixture by distillation using a high-boiling solvent to purify the acrylic acid.
  • the crude product mixture is maintained at a temperature in the range of about 115° C. to about 125° C., including exemplary values of 116° C., 117° C., 118° C., 119° C., 120° C., 121° C., 122° C., 123° C., and 124° C.
  • the temperature can be in a range derived from any two exemplary values.
  • the crude product mixture is maintained at a temperature in the range of about 115° C. to about 120° C.
  • the crude product mixture is maintained at a temperature of about 120° C.
  • the invention further comprises cooling the crude product mixture.
  • the cooling can be accomplished by an intermediate and/or intermittent cooler.
  • cooling can be accomplished by contacting the crude product mixture with the high-boiling solvent, which is of a lower temperature.
  • the contacting can comprise the use of a quench tower.
  • the high-boiling solvent can be described by one or more of the following properties
  • the high-boiling solvent can have a boiling point at least 5° C., or at least 20° C., or at least 30° C. above the dew point of the gaseous product stream, for example 10 to 80° C. or 20 to 80° C. above the dew point of the gaseous product stream at the pressure of distillation.
  • the high-boiling solvent is not an ether, e.g., not diisopropyl ether, or a ketone, e.g. not methyl isobutyl ketone, or other solvent known to form unstable or explosive compounds.
  • the high-boiling solvent comprises an alcohol. In a still further aspect, the high-boiling solvent comprises a linear alcohol. In yet a further aspect, the high-boiling solvent comprises hexanol, heptanol or octanol, or a mixture thereof.
  • the high-boiling solvent comprises a branched alcohol.
  • the high-boiling solvent comprises 2-ethyl hexanol, 2-propyl heptanol, isononanol, isoamyl alcohol, iso-bornyl alcohol, or cyclohexanol, or a mixture thereof.
  • the high-boiling solvent comprises a polyhydric alcohol.
  • the high-boiling solvent comprises ethylene glycol, 1,3-propane diol, 1,3-butane diol, 1,2-butane diol, 2,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,8-octane diol, or 1-9 nonane diol, or a mixture thereof.
  • the high-boiling solvent comprises an amino alcohol.
  • the high-boiling solvent comprises 2-dimethyl aminoethanol, or 2-diethyl aminoethanol, or a mixture thereof.
  • the high-boiling solvent is present in a molar ratio from about 2:1 to about 1:2 (solvent to acrylic acid), for example, 56 mol % of 2-ethyl hexanol and about 43 mol % of acrylic acid, with up to about 1 mol % impurities.
  • the high-boiling solvent can comprise a minimal amount of water.
  • a minimal amount of water is less than 10 wt %, based on the total weight of the high-boiling solvent.
  • a minimal amount of water is less than 5 wt %, based on the total weight of the high-boiling solvent.
  • the amount of water ranges from 0 wt % to 10 wt %, based on the total weight of the high-boiling solvent, including exemplary values of 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, and 9 wt %.
  • the amount of water can be in a range derived from any two exemplary values.
  • the amount of water can range from 0 wt % to 3 wt %, based on the total weight of the high-boiling solvent.
  • the high-boiling solvent can comprise a minimal amount of water in the quench column.
  • the quench column can typically only absorb or take up low amounts of water due to its low affinity of water.
  • the invention further comprises introducing the solvent-acid mixture into a dehydration column at a temperature from about 100° C. to about 120° C., including exemplary values of 101° C., 102° C., 103° C., 104° C., 105° C., 106° C., 107° C., 108° C., 109° C., 110° C., 111° C., 112° C., 113 ° C., 114° C., 115° C., 116° C., 117° C., 118° C., and 119° C.
  • the temperature can be in a range derived from any two exemplary values.
  • the solvent-acid mixture can be introduced into a dehydration column at a temperature from about 105° C. to about 115° C.
  • the solvent-acid mixture is introduced into a dehydration column at a pressure from about 2 bar to 4 bar. In a still further aspect, the solvent-acid mixture is introduced into a dehydration column at a pressure of about 3 bar.
  • the method comprises continuous distillation.
  • the distillation column uses trays in an amount ranging from 40 to 80 theoretical trays, including exemplary values of 41, 42, 43, 44, 45, 46, 47, 48, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, and 79.
  • the trays can be in a range derived from any two exemplary values.
  • the distillation column can use trays in an amount ranging from 50 to 70 theoretical trays.
  • the acrylic acid is obtained with a purity ranging from about 85% to about 99%. In a still further aspect, the acrylic acid is obtained with a purity ranging from about 90% to about 99%. In yet a further aspect, the acrylic acid is obtained with a purity ranging from about 95% to about 99%. In an even further aspect, the acrylic acid is obtained with a purity of about 99%.
  • the method further comprises the addition of an inhibitor.
  • the method comprises adding an inhibitor to the crude product mixture after the formation of the crude product mixture.
  • the inhibitor is added after producing the crude product mixture, but prior to a distillation step.
  • the method comprises adding the inhibitor to the distillation column.
  • the method does not comprise adding an inhibitor prior to the formation of the crude product mixture.
  • the inhibitor acts to prevent acid polymerization.
  • the inhibitor comprises a phenolic derivative. In a still further aspect, the inhibitor comprises hydroquinone, or ethers of hydroquinone, or a mixture thereof.
  • the inhibitor comprises a phenothiazine derivative. In a still further aspect, the inhibitor comprises quinone, or benzoquinone, or a mixture thereof.
  • the inhibitor comprises a metal thiocarbamate. In a still further aspect, the inhibitor comprises copper dibutyldithiocarbamate, copper diethyldithiocarbamate, or copper salicylate, or a mixture thereof.
  • the inhibitor comprises an amine. In a still further aspect, the inhibitor comprises a hydroxylamine or a phenyldiamine, or a mixture thereof.
  • the invention uses the appropriate amount of inhibitor to prevent polymerization.
  • the method comprises inhibitor in the amount ranging from 0.05 wt % to 0.5 wt %, based on the weight of the crude product mixture, including exemplary values of 0.07 wt %, 0.1 wt %, 0.2 wt %, 0.3 wt %, and 0.4 wt %.
  • the amount can be in a range derived from any two exemplary values.
  • the method can comprise an inhibitor in the amount ranging from 0.1 wt % to 0.4 wt %, based on the weight of the crude product mixture.
  • the method comprises an inhibitor in an amount ranging from 10 ppm to 500 ppm, including exemplary values of 25 ppm, 50 ppm, 75 ppm, 100 ppm, 125 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, and 450 ppm.
  • the amount can be in a range derived from any two exemplary values.
  • the method can comprise an inhibitor in an amount ranging from 25 ppm to 400 ppm.
  • the invention further comprises the addition of oxygen.
  • the purification can be conducted in the presence of the atmosphere, an oxygen-enriched atmosphere, or with oxygen bubbled into a liquid stream, for example the crude reaction product.
  • oxygen promotes inhibitor activation.
  • the oxygen promotes the activity of the inhibitor comprising a phenolic derivative or the phenothiazine derivative or a mixture thereof.
  • the invention comprises a method for purifying the crude product mixture by distillation using a low-boiling solvent to purify the acetic acid.
  • the overhead vapor stream is introduced into a counter-current packed absorption column at a temperature from about 30° C. to about 50° C., including exemplary values 32° C., 34° C., 36° C., 38° C., 40° C., 42° C., 44° C., 46° C., and 48° C.
  • the temperature can be in a range derived from any two exemplary values.
  • the overhead vapor stream is introduced at a temperature from about 35° C. to about 45° C.
  • the overhead vapor stream is introduced at a temperature of about 40° C.
  • the overhead vapor stream is introduced into a counter-packed absorption column at a pressure from about 2 to 4 bar. In a still further aspect, the overhead vapor stream is introduced at a pressure of about 3 bar.
  • a low-boiling solvent can be described by one or more of the following properties:
  • the low-boiling solvent comprises isopropyl acetate, or water, or a mixture thereof. In a still further aspect, the low-boiling solvent comprises isopropyl acetate.
  • Other low-boiling solvents are methyl isobutyl ketone, methyl-ethyl ketone, diisopropyl ether, dipropyl ether, di-tert-butyl ether, tert-amyl methyl ether, or ethyl acetate or a mixture thereof.
  • the crude product mixture is maintained at a temperature from about 45° C. to about 70° C., including exemplary values of 47° C., 49° C., 51° C., 53° C., 55° C., 57° C., 59° C., 61° C., 63° C., 65° C., 67° C., and 69° C.
  • the temperature can be in a range derived from any two exemplary values.
  • the crude product mixture is maintained at a temperature from about 50° C. to about 60° C.
  • the crude product mixture is maintained at a temperature from about 55° C. to about 58° C.
  • the crude product mixture is maintained at a temperature of about 57° C.
  • the crude product mixture is routed through an overhead condenser to a decanter.
  • phase splitting occurs at a temperature from about 15° C. to about 45° C., including exemplary values of 16° C., 17 ° C., 18° C., 19° C., 20° C., 21° C., 22° C., 23° C., 24° C., 25° C., 27° C., 29° C., 31° C., 33° C., 35° C., 37° C., 39° C., 40° C., 41° C., 42° C., 43° C., and 44° C.
  • the temperature can be in a range derived from any two exemplary values.
  • phase splitting occurs at a temperature from about 20° C. to about 23° C.
  • phase splitting occurs at a temperature of about 22° C.
  • the method further comprises a side draw from the hetero azeotropic distillation column routed to a purification column to obtain glacial acetic acid. In a further aspect, the method further comprises a side draw from the hetero azeotropic distillation column routed to a distillation column.
  • acetic acid is able to reach concentrations from about 50 wt % to about 90 wt %, based on the crude product mixture, in some of the column trays, including exemplary values of 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %, 80 wt %, and 85 wt %.
  • the weight percentage can be in a range derived from any two exemplary values.
  • acetic acid is able to reach concentrations from about 60 wt % to about 90 wt % in some of the column trays, based on the crude product mixture.
  • acetic acid is able to reach concentrations from about 70 wt % to about 90 wt %, based on the crude product mixture, in some of the column trays. In yet a further aspect, acetic acid is able to reach concentrations from about 75 wt % to about 85 wt % in some of the column trays. In an even further aspect, acetic acid is able to reach concentrations of about 80 wt %, based on the crude product mixture, in some of the column trays.
  • acetic acid is able to reach purities from about 70 wt % to 100 wt %, including exemplary values of 75 wt %, 80 wt %, 85 wt %, 90 wt %, 95 wt %, and 99 wt %.
  • the weight percentage can be in a range derived from any two exemplary values.
  • acetic acid is able to reach purities from about 80 wt % to about 100 wt %.
  • acetic acid is able to reach purities from about 90 wt % to about 100 wt %.
  • acetic acid is able to reach purities from about 95 wt % to about 100 wt %.
  • acetic acid is able to reach purities of about 99 wt %.
  • the invention further comprises addition of an inhibitor to prevent acid polymerization.
  • the inhibitor comprises a phenolic derivative. In a still further aspect, the inhibitor comprises hydroquinone, or ethers of hydroquinone, or a mixture thereof.
  • the inhibitor comprises a phenothiazine derivative. In a still further aspect, the inhibitor comprises quinone, or benzoquinone, or a mixture thereof.
  • the inhibitor comprises a metal thiocarbamate. In a still further aspect, the inhibitor comprises copper dibutyldithiocarbamate, copper diethyldithiocarbamate, or copper salicylate, or a mixture thereof.
  • the inhibitor comprises an amine. In a still further aspect, the inhibitor comprises a hydroxylamine, or a phenyldiamine, or a mixture thereof.
  • the invention further comprises the addition of oxygen for inhibitor activation.
  • the invention comprises a reaction of acrylic acid with the high-boiling solvent to afford an esterification product.
  • the high-boiling solvent is not an ether, e.g. diisopropyl ether, or a ketone, e.g. methyl isobutyl ketone, or other solvent known to form unstable or explosive compounds.
  • the high-boiling solvent comprises an alcohol. In a still further aspect, the high-boiling solvent comprises a linear alcohol. In yet a further aspect, the high-boiling solvent comprises hexanol, heptanol or octanol, or a mixture thereof.
  • the high-boiling solvent comprises a branched alcohol. In a still further aspect, the high-boiling solvent comprises 2-ethyl hexanol.
  • the high-boiling solvent comprises a polyhydric alcohol.
  • the high-boiling solvent comprises ethylene glycol, 1,3-propane diol, or 1,4-butane diol, or a mixture thereof.
  • the high-boiling solvent comprises an amino alcohol.
  • the high-boiling solvent comprises 2-dimethyl aminoethanol or 2-diethyl aminoethanol, or a mixture thereof.
  • esterification reaction conditions include the addition of a strong acid.
  • esterification reaction conditions include the addition of sulfuric acid, p-toulenesulfonic acid, vinyl acidic polymers, or other acidic compounds known in the art to catalyze esterifications of alcohols and acids.
  • esterification reaction conditions include the addition of a strong acid in an amount ranging from about 0.1 wt % to 25 wt %, based on the total weight of the reagents, including exemplary values of 0.4 wt %, 0.6 wt %, 1 wt %, 2 wt %, 4 wt %, 6 wt %, 8 wt %, 10 wt %, 12 wt %, 14 wt %, 16 wt %, 18 wt %, 20 wt %, 22 wt %, and 24 wt %.
  • the amount can be in a range derived from any two exemplary values.
  • the esterification reaction conditions can include the addition of a strong acid in an amount ranging from 1 wt % to 24 wt %, based on the total weight of the reagents.
  • the esterification product can be used in industry.
  • the ester can be used as a fragrance, pharmaceutical composition, a poison, a monomer for polymer synthesis, a flavorant, a perfume, and/or plasticizer.
  • the esterification product comprises an acrylate.
  • the esterification product has a purity ranging from 75 wt % to 99.9 wt %, including exemplary values of 77 wt %, 79 wt %, 81 wt %, 83 wt %, 85 wt %, 87 wt %, 89 wt %, 90 wt %, 91 wt %, 93 wt %, 94 wt %, 95 wt %, 96 wt %, 97 wt %, 98 wt %, 99 wt %, and 99.5 wt %.
  • the purity can be in a range derived from any two exemplary values.
  • the esterification product can have a purity ranging from 90 wt % to 99.9 wt %.
  • the acrylate formed can be isolated by selecting the appropriate fraction from the esterification column using standard techniques.
  • unreacted acrylic acid and the high-boiling solvent can be recovered. In a still further aspect, unreacted acrylic acid and the high-boiling solvent can be recycled.
  • gaseous stream 10 comes from the acrylic acid reactor after cooling.
  • the acrylic acid reactor not shown in the FIGURE, is based on catalytic propane oxidation.
  • the acrylic acid reactor can also be based on conventional catalytic propylene oxidation.
  • Stream 10 can be at about 120° C. and 3 Bar pressure and can contain acetic acid, acrylic acid, unreacted propane, and/or oxygen.
  • Stream 10 can also contains byproducts like water, ethane, propylene, butanes, and a small amount of miscellaneous impurities which can include propionic acid, formic acid, acetone, acetaldehyde, acrolein, and/or furfural.
  • Stream 10 can be fed to the bottom of the absorption column C 10 .
  • Absorption column C 10 can be a packed column and/or a tray column design.
  • Liquid stream 11 can be rich in 2-ethylhexanol and at about 95° C., can be fed at the top of the column C 10 .
  • Stream 10 and stream 11 can flow counter currently in the column and can come in contact over the packing surface and/or the trays.
  • the liquid stream 11 flowing down in the column C 10 can selectively absorb more than 95% of the incoming acrylic acid. This liquid stream 11 also can absorb other components but in significantly lower fractions.
  • Liquid stream 13 can leave from the bottom of the column C 10 at about 120° C. and can be cooled to about 50° C. in the heat exchanger E 20 .
  • a cold liquid stream 18 from heat exchanger E 20 can be fed to the distillation column C 30 .
  • the distillation column C 30 can operate under vacuum and can be designed to maximize the separation of acrylic acid and 2-ethylhexanol at the bottom of the column.
  • Liquid stream 20 can be drawn from bottom of the column C 30 .
  • the stream 20 can contain acrylic acid, 2-ethylhexanol, and/or small impurities. This stream 20 can be sent to 2-ethylhexyl acrylate production and/or acrylic acid separation. Acrylic acid and/or 2-ethylhexanol can be separated using conventional distillation technique.
  • a small distillate stream 21 can be drawn from the top of the column C 30 which can mainly contain acetic acid, acrylic acid, and/or water. This stream 21 can be subjected to further separation of the acids by conventional distillation and/or by crystallization. Vapor stream 19 drawn from top of the column C 30 can be fed to distillation column C 40 . Stream 19 can mainly contain acetic acid, acrylic acid, propane, and/or water vapors.
  • Vapor stream 12 from the top of the column C 10 can be cooled from about 121° C. to about 40° C. in the heat exchanger E 10 .
  • the cooled stream 14 from E 10 can be fed to the bottom of the absorption column C 20 .
  • Liquid stream 15 can be at about 22° C. and rich in isopropyl acetate. Liquid stream 15 can be fed at the top of the column C 20 .
  • Stream 14 and stream 15 can come in contact counter currently in the column C 20 which can be filled with packing and/or trays.
  • Column C 20 can operate at about 2 Bar pressure.
  • Acetic acid, acrylic acid, and/or 2-ethylhexanol carried in stream 14 can be absorbed in the liquid steam flowing down in the column C 20 and leaves as stream 17 from the bottom of the column.
  • the stream 17 at about 32° C. can be fed to the distillation column C 40 .
  • the vapor stream 16 can leave from the top of the column C 20 at about 30° C.
  • Stream 16 can mainly contain propane, isopropyl acetate, and/or some non-condensable gases like propylene, CO 2 , CO, and/or oxygen.
  • Stream 16 can be sent for further processing for isopropyl acetate, propane, and/or propylene recovery. Propane and/or propylene can be sent back to acrylic acid reactor.
  • Distillation column C 40 can operate at about 1 Bar pressure and can be designed to separate 2-ethylhexanol, isopropyl acetate, and/or acetic acid.
  • Liquid stream 25 can be drawn from bottom of column C 40 at about 157° C.
  • Stream 25 can mainly contain 2-ethylhexanol with a concentration of more than 91% on weight basis.
  • Stream 25 can be further mixed with stream 28 and form a stream 11 . Both streams 28 and 11 are described earlier.
  • Vapor stream 22 can be drawn from top of the column C 40 which can be rich in isopropyl acetate with a concentration of more than 84% on weight basis.
  • Stream 22 can be cooled in the heat exchanger E 30 to a temperature of about 22° C.
  • the cooled stream 29 from heat exchanger E 30 can be fed to a three phase separator S 10 .
  • the isopropyl acetate solvent stream 33 can also be fed into S 10 .
  • the organic phase can be separated from S 10 as stream 31 which can be rich in isopropyl acetate with a concentration of more than 91% on weight basis.
  • Stream 31 can be divided into two streams: stream 23 and stream 34 .
  • Stream 23 can be used as a reflux for distillation column C 40 .
  • Stream 23 can be about 79% of the stream 31 .
  • the distillate stream can be further divided into two streams: stream 15 and stream 35 .
  • Stream 15 can be about 67% of stream 34 which can be fed to column C 20 .
  • Stream 35 can be sent for isopropyl acetate recovery.
  • the vapor stream 30 from S 10 can be combined with stream 16 for further treatment.
  • Aqueous stream 32 from S 10 can be sent for stripping and recovery of organics and/or the water can be
  • Stream 26 can be drawn as a side stream from distillation column C 40 .
  • Stream 26 can have an acetic acid concentration of about 86% on weight basis.
  • Stream 26 can be fed to distillation column C 50 for acetic acid purification. Pure acetic acid can be recovered as distillate from the top of the column as stream 27 with a purity of more than 99.5% on weight basis.
  • Distillation column C 50 can be operated at about 2 Bar pressure.
  • Stream 24 can be drawn from the bottom of C 50 and fed back to the bottom of distillation column C 40 .
  • aspects of the present invention disclose one or more methods for the purification of acetic acid and acrylic acid from a crude product mixture.
  • the product mixture can result, for example, from the partial oxidation reaction of propane over a mixed metal catalyst.
  • the invention includes at least the following aspects:
  • a method for purifying an acid comprising:
  • Aspect 2 The method according to aspect 1, further comprising the reaction of acrylic acid with the high-boiling solvent to produce an acrylate.
  • Aspect 3 The method according to any of aspects 1 and 2, further comprising an inhibitor to prevent acid polymerization.
  • Aspect 4 The method according to aspect 3, wherein the inhibitor comprises a phenolic derivative.
  • Aspect 5 The method according to aspect 3, wherein the inhibitor comprises hydroquinone, or ethers of hydroquinone, or a mixture thereof.
  • Aspect 6 The method according to aspect 3, wherein the inhibitor comprises a phenothiazine derivative.
  • Aspect 7 The method according to aspect 3, wherein the inhibitor comprises quinone, or benzoquinone, or a mixture thereof.
  • Aspect 8 The method according to aspect 3, wherein the inhibitor comprises a metal thiocarbamate.
  • Aspect 9 The method according to aspect 3, wherein the inhibitor comprises copper dibutyldithiocarbamate, copper diethyldithiocarbamate, or copper salicylate, or a mixture thereof.
  • Aspect 10 The method according to aspect 3, wherein the inhibitor comprises an amine.
  • Aspect 11 The method according to aspect 3, wherein the inhibitor comprises a hydroxylamine, or a phenyldiamine, or a mixture thereof.
  • Aspect 12 The method according to any of aspects 1-11, further comprising the addition of oxygen for inhibitor activation.
  • Aspect 13 The method according to any of aspects 1-12, wherein the high-boiling solvent comprises an alcohol.
  • Aspect 14 The method according to any of aspects 1-12, wherein the high-boiling solvent comprises a linear alcohol.
  • Aspect 15 The method according to any of aspects 1-12, wherein the high-boiling solvent comprises hexanol, heptanol or octanol, or a mixture thereof.
  • Aspect 16 The method according to any of aspects 1-12, wherein the high-boiling solvent comprises a branched alcohol.
  • Aspect 17 The method according to any of aspects 1-12, wherein the high-boiling solvent comprises 2-ethyl hexanol.
  • Aspect 18 The method according to any of aspects 1-12, wherein the high-boiling solvent comprises a polyhydric alcohol.
  • Aspect 19 The method according to any of aspects 1-12, wherein the high-boiling solvent comprises ethylene glycol, 1,3-propane diol, or 1,4-butane diol, or a mixture thereof.
  • Aspect 20 The method according to any of aspects 1-12, wherein the high-boiling solvent comprises an amino alcohol.
  • Aspect 21 The method according to any of aspects 1-12, wherein the high-boiling solvent comprises 2-dimethyl aminoethanol, or 2-diethyl aminoethanol, or a mixture thereof.
  • Aspect 22 The method according to any of aspects 1-21, wherein the low-boiling solvent comprises isopropyl acetate, or water, or a mixture thereof.
  • Aspect 23 The method according to any of aspects 1-22, wherein the partial oxidation reaction comprises propane as the starting material and a Mo—V—Ga—Pd—Nb—X mixed metal catalyst, wherein X is La, Te, Ge, Zn, Si, In or W
  • Aspect 24 The method according to any of aspects 1-23, wherein the method further comprises the high-boiling solvent reacting downstream of the acrylic acid purification with the acrylic acid to form a specialty acrylate.
  • Aspect 25 The method according to any of aspects 1-24, wherein the crude product mixture further comprises water.
  • Aspect 26 The method according to any of aspects 1-25, wherein the method comprises at least two separate distillation steps.
  • Table 1 is included as a prophetic example to show the mass balance in FIG. 1 .
  • Table 1 was prepared using Aspen Plus V7.3.

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WO2017114831A1 (en) * 2015-12-29 2017-07-06 Shell Internationale Research Maatschappij B.V. Process for converting alkanes and/or alkenes to alkenes and carboxylic acids
KR102079775B1 (ko) * 2016-11-25 2020-02-20 주식회사 엘지화학 (메트)아크릴산의 연속 회수 방법 및 장치
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Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2748159A (en) 1952-09-08 1956-05-29 Goodyear Tire & Rubber Purification and decolorization of esters
GB783463A (en) 1955-05-10 1957-09-25 Distillers Co Yeast Ltd Esters purification process
US2862958A (en) 1955-10-13 1958-12-02 Hercules Powder Co Ltd Method of improving electrical properties of plasticizers by treatment with magnesium silicate
GB813867A (en) 1956-12-27 1959-05-27 Distillers Co Yeast Ltd Purification of esters of dicarboxylic acids
GB1058242A (en) 1962-06-29 1967-02-08 Beck Koller And Company Englan Process for the production of esters
US3433831A (en) 1965-06-30 1969-03-18 Asahi Chemical Ind Separation and purification of acrylic acid from acetic acid by solvent extraction and azeotropic distillation with a two component solvent-entrainer system
US3459736A (en) 1963-09-03 1969-08-05 Reichhold Chemicals Inc Organic esters prepared with the use of a titanium peroxide-containing catalyst,said ester being suitable for use as a plasticizer for organic film-forming materials and method of preparing such esters
GB1182809A (en) 1966-11-14 1970-03-04 Celanese Corp Recovery of Acrylic Acid.
US3666632A (en) 1968-10-08 1972-05-30 Asahi Chemical Ind Method for the separation of acrylic acid from aqueous solution containing acrylic acid and acetic acid
JPS497216A (enrdf_load_stackoverflow) 1972-05-24 1974-01-22
JPS4995918A (enrdf_load_stackoverflow) 1973-01-24 1974-09-11
JPS4946942B1 (enrdf_load_stackoverflow) 1971-04-05 1974-12-12
JPS5011364A (enrdf_load_stackoverflow) 1973-05-30 1975-02-05
JPS62267341A (ja) 1986-05-16 1987-11-20 Mitsubishi Kasei Vinyl Co 可塑剤の製造法
JPH0341051A (ja) 1989-07-07 1991-02-21 Idemitsu Petrochem Co Ltd アクリル酸エステル又はメタクリル酸エステルの製造方法
US5198580A (en) 1991-11-18 1993-03-30 The Standard Oil Company Process for oxidation of propane
EP0551111A1 (en) 1992-01-09 1993-07-14 Nippon Shokubai Co., Ltd. Process for purifying acrylic acid to high purity in the production of acrylic acid
US5243069A (en) * 1981-12-11 1993-09-07 Rohm And Haas Company Ester of Michael addition homopolymers of acrylic acid
JPH05246941A (ja) 1992-01-09 1993-09-24 Nippon Shokubai Co Ltd アクリル酸製造においてアクリル酸を高純度に精製する方法
JPH0948744A (ja) 1995-08-04 1997-02-18 Showa Denko Kk 酢酸の精製方法
JPH09151158A (ja) 1995-09-29 1997-06-10 Showa Denko Kk 酢酸の精製方法
JPH09263566A (ja) 1996-03-29 1997-10-07 Cosmo Sogo Kenkyusho:Kk 粗ベンゼンジカルボン酸の精製方法、精製に使用する触媒およびその製造方法
US5785821A (en) 1995-12-05 1998-07-28 Nippon Shokubai Co., Ltd. Process for the production of acrylic acid
EP0861820A2 (en) 1997-02-28 1998-09-02 Nippon Shokubai Co., Ltd. Method for recovering acrylic acid
JPH10306052A (ja) 1997-05-08 1998-11-17 Nippon Shokubai Co Ltd アクリル酸の回収方法
US5880310A (en) 1997-05-21 1999-03-09 Mitsubishi Gas Chemical Company, Inc. Process for producing plasticizer esters
US5910607A (en) 1994-08-04 1999-06-08 Mitsubishi Chemical Corp. Process for producing acrylic acid
CN1270952A (zh) 1999-03-31 2000-10-25 株式会社日本触媒 (甲基)丙烯酸的精制方法
US6160162A (en) 1998-11-16 2000-12-12 Saudi Basic Industries Corporation Methods of catalytic oxidation of propane to acrylic acid
US6352619B1 (en) * 1996-09-16 2002-03-05 Atofina Method for purifying acrylic acid
US6399817B1 (en) 1999-03-05 2002-06-04 Rohm And Haas Company Process for preparing (meth)acrylic acid
WO2005021482A1 (en) 2003-08-29 2005-03-10 Exxonmobil Chemical Patents Inc. Improvements in or relating to phthalate plasticiser esters
CN1625544A (zh) 2002-01-29 2005-06-08 三菱化学株式会社 (甲基)丙烯酸的制造方法
JP2005179352A (ja) 2003-11-28 2005-07-07 Mitsubishi Chemicals Corp （メタ）アクリル酸の精製方法
JP2005232008A (ja) 2001-12-27 2005-09-02 Mitsubishi Chemicals Corp （メタ）アクリル酸の蒸留方法
CN1697818A (zh) 2003-11-28 2005-11-16 三菱化学株式会社 (甲基)丙烯酸的提纯方法
JP2005320302A (ja) 2004-05-11 2005-11-17 New Japan Chem Co Ltd ジカルボン酸ジエステルの製造方法
JP3832868B2 (ja) 1994-07-27 2006-10-11 三菱化学株式会社 アクリル酸の精製法
JP2006316066A (ja) 2006-06-19 2006-11-24 Nippon Shokubai Co Ltd （メタ）アクリル酸および／またはそのエステルの蒸留方法
CN1884249A (zh) 2006-07-11 2006-12-27 天津天溶化工有限公司 邻苯二甲酸二辛酯清洁生产方法
JP3937495B2 (ja) 1997-02-28 2007-06-27 株式会社日本触媒 アクリル酸の回収方法
US7321058B2 (en) * 2000-06-14 2008-01-22 Basf Aktiengesellschaft Method for producing acrolein and/or acrylic acid
CN101269899A (zh) 2008-05-13 2008-09-24 吉林大学 一种丙烯酸废水的综合处理方法
CN101367720A (zh) 2008-09-18 2009-02-18 中国石油大学(华东) 一种隔壁共沸精馏塔提纯丙烯酸的工艺方法及装置
CN101530780A (zh) 2009-04-21 2009-09-16 浙江工商大学 一种两步分离提纯柱及其应用
US7622607B2 (en) 2003-11-04 2009-11-24 Arkema France Method for purifying (meth)acrylic acid obtained by oxidizing a gaseous substrate
JP4809532B2 (ja) 1999-11-15 2011-11-09 サウディ ベーシック インダストリーズ コーポレイション プロパンのアクリル酸への接触酸化用触媒、その製造法及び使用法
US20160096798A1 (en) 2013-06-07 2016-04-07 Sabic Basic Industries Corporation Method for purifying dioctyl phthalate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5011364B1 (enrdf_load_stackoverflow) * 1965-06-30 1975-04-30
US3422831A (en) * 1967-02-20 1969-01-21 Gen Electric Turbine control system

Patent Citations (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2748159A (en) 1952-09-08 1956-05-29 Goodyear Tire & Rubber Purification and decolorization of esters
GB783463A (en) 1955-05-10 1957-09-25 Distillers Co Yeast Ltd Esters purification process
US2862958A (en) 1955-10-13 1958-12-02 Hercules Powder Co Ltd Method of improving electrical properties of plasticizers by treatment with magnesium silicate
GB813867A (en) 1956-12-27 1959-05-27 Distillers Co Yeast Ltd Purification of esters of dicarboxylic acids
GB1058242A (en) 1962-06-29 1967-02-08 Beck Koller And Company Englan Process for the production of esters
US3459736A (en) 1963-09-03 1969-08-05 Reichhold Chemicals Inc Organic esters prepared with the use of a titanium peroxide-containing catalyst,said ester being suitable for use as a plasticizer for organic film-forming materials and method of preparing such esters
US3433831A (en) 1965-06-30 1969-03-18 Asahi Chemical Ind Separation and purification of acrylic acid from acetic acid by solvent extraction and azeotropic distillation with a two component solvent-entrainer system
GB1182809A (en) 1966-11-14 1970-03-04 Celanese Corp Recovery of Acrylic Acid.
US3666632A (en) 1968-10-08 1972-05-30 Asahi Chemical Ind Method for the separation of acrylic acid from aqueous solution containing acrylic acid and acetic acid
JPS4946942B1 (enrdf_load_stackoverflow) 1971-04-05 1974-12-12
JPS497216A (enrdf_load_stackoverflow) 1972-05-24 1974-01-22
JPS4995918A (enrdf_load_stackoverflow) 1973-01-24 1974-09-11
JPS5011364A (enrdf_load_stackoverflow) 1973-05-30 1975-02-05
US5243069A (en) * 1981-12-11 1993-09-07 Rohm And Haas Company Ester of Michael addition homopolymers of acrylic acid
JPS62267341A (ja) 1986-05-16 1987-11-20 Mitsubishi Kasei Vinyl Co 可塑剤の製造法
JPH0341051A (ja) 1989-07-07 1991-02-21 Idemitsu Petrochem Co Ltd アクリル酸エステル又はメタクリル酸エステルの製造方法
US5198580A (en) 1991-11-18 1993-03-30 The Standard Oil Company Process for oxidation of propane
EP0551111A1 (en) 1992-01-09 1993-07-14 Nippon Shokubai Co., Ltd. Process for purifying acrylic acid to high purity in the production of acrylic acid
JPH05246941A (ja) 1992-01-09 1993-09-24 Nippon Shokubai Co Ltd アクリル酸製造においてアクリル酸を高純度に精製する方法
JP3832868B2 (ja) 1994-07-27 2006-10-11 三菱化学株式会社 アクリル酸の精製法
US5910607A (en) 1994-08-04 1999-06-08 Mitsubishi Chemical Corp. Process for producing acrylic acid
JPH0948744A (ja) 1995-08-04 1997-02-18 Showa Denko Kk 酢酸の精製方法
JPH09151158A (ja) 1995-09-29 1997-06-10 Showa Denko Kk 酢酸の精製方法
US5785821A (en) 1995-12-05 1998-07-28 Nippon Shokubai Co., Ltd. Process for the production of acrylic acid
JPH09263566A (ja) 1996-03-29 1997-10-07 Cosmo Sogo Kenkyusho:Kk 粗ベンゼンジカルボン酸の精製方法、精製に使用する触媒およびその製造方法
US6352619B1 (en) * 1996-09-16 2002-03-05 Atofina Method for purifying acrylic acid
EP0861820A2 (en) 1997-02-28 1998-09-02 Nippon Shokubai Co., Ltd. Method for recovering acrylic acid
JP3937495B2 (ja) 1997-02-28 2007-06-27 株式会社日本触媒 アクリル酸の回収方法
JPH10306052A (ja) 1997-05-08 1998-11-17 Nippon Shokubai Co Ltd アクリル酸の回収方法
US5880310A (en) 1997-05-21 1999-03-09 Mitsubishi Gas Chemical Company, Inc. Process for producing plasticizer esters
US6160162A (en) 1998-11-16 2000-12-12 Saudi Basic Industries Corporation Methods of catalytic oxidation of propane to acrylic acid
CN1145527C (zh) 1998-11-16 2004-04-14 沙地基本工业公司 丙烷催化氧化成丙烯酸的催化剂及其制造和使用方法
US6399817B1 (en) 1999-03-05 2002-06-04 Rohm And Haas Company Process for preparing (meth)acrylic acid
CN1270952A (zh) 1999-03-31 2000-10-25 株式会社日本触媒 (甲基)丙烯酸的精制方法
JP4809532B2 (ja) 1999-11-15 2011-11-09 サウディ ベーシック インダストリーズ コーポレイション プロパンのアクリル酸への接触酸化用触媒、その製造法及び使用法
US7321058B2 (en) * 2000-06-14 2008-01-22 Basf Aktiengesellschaft Method for producing acrolein and/or acrylic acid
JP2005232008A (ja) 2001-12-27 2005-09-02 Mitsubishi Chemicals Corp （メタ）アクリル酸の蒸留方法
CN1625544A (zh) 2002-01-29 2005-06-08 三菱化学株式会社 (甲基)丙烯酸的制造方法
WO2005021482A1 (en) 2003-08-29 2005-03-10 Exxonmobil Chemical Patents Inc. Improvements in or relating to phthalate plasticiser esters
CN1835908A (zh) 2003-08-29 2006-09-20 埃克森美孚化学专利公司 邻苯二甲酸酯增塑剂酯或其相关方面的改进
US7622607B2 (en) 2003-11-04 2009-11-24 Arkema France Method for purifying (meth)acrylic acid obtained by oxidizing a gaseous substrate
CN1697818A (zh) 2003-11-28 2005-11-16 三菱化学株式会社 (甲基)丙烯酸的提纯方法
JP2005179352A (ja) 2003-11-28 2005-07-07 Mitsubishi Chemicals Corp （メタ）アクリル酸の精製方法
JP2005320302A (ja) 2004-05-11 2005-11-17 New Japan Chem Co Ltd ジカルボン酸ジエステルの製造方法
JP2006316066A (ja) 2006-06-19 2006-11-24 Nippon Shokubai Co Ltd （メタ）アクリル酸および／またはそのエステルの蒸留方法
CN1884249A (zh) 2006-07-11 2006-12-27 天津天溶化工有限公司 邻苯二甲酸二辛酯清洁生产方法
CN101269899A (zh) 2008-05-13 2008-09-24 吉林大学 一种丙烯酸废水的综合处理方法
CN101367720A (zh) 2008-09-18 2009-02-18 中国石油大学(华东) 一种隔壁共沸精馏塔提纯丙烯酸的工艺方法及装置
CN101530780A (zh) 2009-04-21 2009-09-16 浙江工商大学 一种两步分离提纯柱及其应用
US20160096798A1 (en) 2013-06-07 2016-04-07 Sabic Basic Industries Corporation Method for purifying dioctyl phthalate

Non-Patent Citations (38)

* Cited by examiner, † Cited by third party
Title
"Acrylic Acid and Derivatives"; Kirk Othmer Encyclopedia of Chemical Technology; 2003, vol. 1; p. 342-369.
"Acrylic Acid", Chemsystems PERP program, PERP 08/09, Nexant, 2010, 7 pages.
Chinese Patent No. 101269899; Date of Publication: Sep. 24, 2008; Abstract Only; 1 page.
Chinese Patent No. 101367720; Date of Publication: Feb. 18, 2009; Abstract Only; 1 page.
Habib, Rowshanul and Karim, M. Rezaul, "Antimicrobial and Cytotoxic Activity of Di-(2-ethylhexyl) Phthalate and Anhydrosophoradiol-3-acetate Isolated from Calotropis gigantea (Linn.) Flower", Mycobiology (Mar. 2009);37(1): 31-36.
Huang, G. et al., "Isobaric Vapor-Liquid Equilibrium for Binary Systems of Toluene + Acrylic Acid, Toluene + Acetic Acid, and Cyclohexane + Acrylic Acid at 20 kPa"; J.Chem.Eng. Data, 2011, vol. 56, pp. 3914-3919.
International Preliminary Report on Patentability, PCT/IB2014/061953, Issued Dec. 17, 2015.
International Preliminary Report on Patentability, PCT/US2014/038573, Issued Dec. 3, 2015.
International Search Report and Written Opinion, Mailed Sep. 24, 2014.
International Search Report and Written Opinion, PCT/US2014/038573, issued Nov. 13, 2014.
International Search Report for PCT/US2014/038573 (KS30054PCT) mailed Nov. 13, 2014, 5 pages.
International Search Report of the International Searching Authority for PCT/IB2014/061953 mailed Sep. 24, 2014, 5 pages.
Japanese Patent No. 2005179352; Date of Publication: Jul. 7, 2005; Abstract Only; 1 page.
Japanese Patent No. 2005232008; Date of Publication: Sep. 2, 2005; English Translation, 5 pages.
Japanese Patent No. 2006316066; Date of Publication: Nov. 24, 2006; Abstract Only; 2 pages.
Japanese Patent No. 3832868; Date of Publication: Oct. 11, 2006; Abstract Only; 1 page.
Japanese Patent No. 3937495; Date of Publication: Jun. 27, 2007; Abstract Only; 1 page.
Japanese Patent No. 4809532; Date of Publication: Nov. 9, 2011; Machine Translation, 13 pages.
Japanese Patent No. H0341051; Date of Publication: Feb. 21, 1991; Abstract Only; 1 page.
Japanese Patent No. H05246941; Date of Publication: Sep. 24, 1993; Abstract Only; 2 pages.
Japanese Patent No. H09151158; Date of Publication: Jun. 10, 1997; Machine Translation, 18 pages.
Japanese Patent No. H0948744; Date of Publication: Feb. 18, 1997; Abstract Only; 1 page.
Japanese Patent No. H10306052; Date of Publication: Nov. 17, 1998; Abstract Only; 1 page.
Japanese Patent No. S46020372; Date of Publication: Jun. 8, 1971; Machine Translation, 8 pages.
Japanese Patent No. S4634692; Date of Publication: Oct. 11, 1971; Machine Translation, 10 pages.
Japanese Patent No. S4946942; Date of Publication: Dec. 12, 1974; English Translation, 5 pages.
Japanese Patent No. S497216; Date of Publication: Jan. 22, 1974; Machine Translation, 6 pages.
Japanese Patent No. S4995918; Date of Publication: Sep. 11, 1974; Machine Translation, 7 pages.
Japanese Patent No. S5011364; Date of Publication: Apr. 30, 1975; Machine Translation, 6 pages.
Sastry, V.M.V.S. and Rao, G.R.K., "Dioctyl phthalate, and antibacterial compound from the marine brown alga-Sargassum wightii", Journal of Applied Phycology, 7: 185-186 (1995).
Sastry, V.M.V.S. and Rao, G.R.K., "Dioctyl phthalate, and antibacterial compound from the marine brown alga—Sargassum wightii", Journal of Applied Phycology, 7: 185-186 (1995).
Torane, Rasika C., et al., "Isolation and Characterisation of 1, 2 Benzenedicarboxylic acid, bis (2 ethylhexyl) ester-Dioctyl Phthalate, a Bioactive Compound from Ehretia laevis", Journal of Pharm. Research (2012) 5(6), 3251-3252.
Torane, Rasika C., et al., "Isolation and Characterisation of 1, 2 Benzenedicarboxylic acid, bis (2 ethylhexyl) ester—Dioctyl Phthalate, a Bioactive Compound from Ehretia laevis", Journal of Pharm. Research (2012) 5(6), 3251-3252.
Unknown Author, "Dioctyl Phthtalate", XP-002728241, Jun. 3, 2013, retrieved from the Internet: UURL: https://chemicalland21.com/industrialchem/plasticizer/DOP.htm, 3 pages.
Written Opinion of the International Searching Authority for PCT/IB2014/061953 mailed Sep. 24, 2014, 9 pages.
Written Opinion of the International Searching Authority for PCT/US2014/038573 (KS30054PCT) mailed Nov. 13, 2014, 6 pages.
Xu, Leilei, et al., "Carbon dioxide reforming of methane over ordered mesoporous NiO-MgO-Al2O3 composite oxides", Applied Catalysis B: Environmental 108-109 (2011) p. 177-190.
Xu, Leilei, et al., "Carbon dioxide reforming of methane over ordered mesoporous NiO—MgO—Al2O3 composite oxides", Applied Catalysis B: Environmental 108-109 (2011) p. 177-190.

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AU2014268860A1 (en) 2015-10-22
KR20160009598A (ko) 2016-01-26
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JP2016520096A (ja) 2016-07-11
CN105263895A (zh) 2016-01-20
CA2908710A1 (en) 2014-11-27

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